ELIMINATION

Traya, Levie Grace M.

INTRODUCTION
The dehydration of alcohol is an
important elimination reaction that
takes place under acidic rather
than basic condition. It involves an
E1 mechanism. The function of the
acidic reagent is to convert the
hydroxyl group to a better leaving
group by protonation.
This elimination reaction is the
reverse
of
acid-catalyzed
hydration. Because a carbocation
or closely related species is the
intermediate, the elimination step
would be expected to favor the
more substituted alkene. The E1
mechanism also explains the
general trend in relative reactivity.
Tertiary alcohols are the most
reactive, and reactivity decreases
going to secondary and primary
alcohol. Also in accord with E1
mechanism is the fact that
rearranged products are found in
cases
where
a
carbocation
intermediate would be expected to
rearrange.
For many alcohols, exchange of
the hydroxyl group with solvent
competes with dehydration. This
exchange
indicates
that
the
carbocation can undergo SN1
capture
in
competition
with

elimination.
Under
conditions
where proton removal is ratedetermining, it would be expected
that significant isotope effect would
be seen. This is, in fact, observed.

In connection to the facts stated

this experiment aims to understand
the concept of elimination and
synthesize an alkene from an
alcohol and test it using potassium
permanganate test and bromine
test.

METHODOLOGY
a. Materials
This experiment will use the
following: (a) tert-butyl alcohol, (b)
con. H2SO4 , (c) CaCl2, (d) acetone,
(e) 1% aqueous KMnO4, (f) carbon
tetrachloride, (g) 2% bromine, (h)
separatory
funnel,
(i)
glass
dropper,
(j)
250-mL
roundbottomed flask, (k) pipet, (l)
aspirator, (m) thermometer, (n)
Reflux condenser (Relfux set-up),
(o) Iron ring, (p) thermometer
holder, (q) alcohol lamp, and (r)
wire gauze.
b. Procedure

In this experiment you will be

using tert-butyl alcohol which melts
at
25-25.5 .
It
is
more
convenient
to
handle
t-butyl
alcohol as liquid; if your laboratory
is not warm enough to melt the
alcohol
naturally;
it
is
recommended that it be liquefied
by placing the container in a pan of
warm water.
In a 250-mL round-bottom flask,
place 14 mL water and add
cautiously, with swirling, 14 mL
concentrated sulfuric acid. Cool the
diluted acid to about 50 and
slowly add 12.6 mL of t-butyl
alcohol. Attach once a reflux
condenser and boil the material
gently for 45 mins.
Cool the reaction mixture to room
temperature, transfer it to a
separatory funnel, and carefully
draw off the aqueous acid layer.
Wash the hydrocarbon layer with
water to remove traces of acid and
dry it with about 1 g anhydrous
calcium chloride. Transfer the dry
liquid into a flask arranged for
distillation, collecting the fraction
at 100 -108 .
Carry out the bromine and
potassium permanganate test for
unsaturation. Submit the remaining
product to the instructor in a
labeled vial.

Potassium Permanganate Test

In a small test tube dissolve 3
drops of the alkene product in 1 mL
of
alcohol-free
acetone.
Add
dropwise, with vigorous shaking, a
1% aqueous solution of potassium
permanganate. A positive test is
the loss within 1 minute of the
purple permanganate ion color and
formation of the insoluble brown
hydrated oxides of manganese.
Bromine Test
This test should be carried out in
a hood. In a small test tube
dissolve 3 drops of the alkene
product
in
1
mL
carbon
tetrachloride, and ddd dropwise,
with shaking, 2% solution of
bromine in carbon tetrachloride. A
positive test is the loss of brown
color.

DISCUSSION
Many secondary and tertiary
halides undergo E1 elimination in
competition with the SN1 reaction
in neutral or acidic solutions. For
this experiment, when tert-butyl
alcohol solvolyzes in sulfuric acid it
will produce diisobutylene by
elimination.
Alcohols
and
ethers
rarely
undergo substitution or elimination
unless strong acid is present. The
acid is necessary to convert a
relatively poor leaving group, OH

for this particular experiment, into

a relatively good one, H2O. Thus
the dehydration of alcohols to
alkenes
is
an
acid-catalyzed
reaction requiring strong acids. In
this
experiment,
the
starting
material is an alcohol, tert-butyl
alcohol, was reacted to an acid,
sulfuric
acid,
to
produce
diisobutylene.
In the reaction, the starting
material will react with sulfuric acid
where the acid converted the poor
leaving group OH into H2O which is
a better leaving group. The leaving
group will cleave out producing the
carbocation where it will be
attacked by the base. The base
removes a beta-proton, leaving
behind its bonding electrons to
form the new double bond. Further
reaction
gives
a
product
diisobutylene at a rate independent
of
the
water
concentration.
Diisobutylene was will be produced
because isobutylene is an unstable
product and thus react furthermore
with the carbocation being created.
The alcohol is the product of an
SN1 reaction and the alkene is the
product of the E1 reaction. The
characteristics
of
these
two
reaction mechanisms are similar,
as expected. They both show first
order kinetics; neither is much
influenced by a change in the
nucleophile/base; and both are
relatively non-stereospecific.

To summarize, when carbocation

intermediates are formed, one can
expect them to react further by
one or more of the following
modes:
1.

The cation may bond to

a nucleophile to give a
substitution product.
2. The
cation
may
transfer a beta-proton to a
base,
giving
an
alkene
product.
3. The
cation
may
rearrange to a more stable
carbocation, and then react
by mode #1 or #2.
Since the SN1 and E1 reactions
precede via the same carbocation
intermediate, the product ratios are
difficult to control and both
substitution and elimination usually
take place.
The hydrocarbon will be subjected
to two confirmatory tests namely
potassium permanganate test and
bromine test.
For bromide test, the brown
solution become colorless that
might indicate a positive test
affirming the presence of alkene.
When the bromine test for the
alkene crude product is positive, it
is because bromine and the alkene
forms a double bond that are open
for an attack since bromine is
electron deficient and the elkene
have pi electrons. Due to their C=C
double bonds which can be broken,

alkenes react readily with bromine

to
produce
saturated
dibromoalkanes. In the presence of
Br2 or Br-Br (which is red/brown),
the Br-Br bond attacks the double
bond forming C-Br new bonds. Thus
the red/brown color disappears.
In the potassium test, the violet
solution will turn into a brown
insoluble solution. Under acidic
conditions, the manganate(VII) ions
will be reduced to manganese(II)
ions. Under alkaline conditions, the
manganate(VII)
ions
will
first
reduce to green manganate(VI)
ions and then further to dark brown
solid
manganese(IV)
oxide
(manganese dioxide). The last
reaction is also the one that would
be obtain if the reaction was done
under neutral conditions. It can be
observe in the reaction there are
neither
hydrogen
ions
nor
hydroxide ions on the left-hand
side of the equation.

REFERRENCE
Books

Bruice, Paula Y. Organic Chemistry.

4th ed. Pearson Prentice Hall. 2004
Boyd,
R. N. & Morrison,
R.T.
Organic Chemistry. 6th Ed. Prentice
Hall. 1992
Carey,
Francis
A.
Organic
th
Chemistry. 4
ed. McGraw-Hill.
2000
Chang, Reymond. Chemistry. 10th
ed. McGraw-Hill. 2010
McMury,
John.Organic.
th
Chemistry.8
ed.
Brooks/Cole,
Cengage Learning. 2012

Web
E1 Reaction. ChemWiki. Retrieved
on
10
April
2015,
from
http://chemwiki.ucdavis.edu/Organi
c_Chemistry/Reactions/E1_Reaction
Elimination
reactios.
CHIME.
Retrieved on 10 April 2015, from
http://www.mhhe.com/physsci/che
mistry/carey/student/olc/graphics/c
arey04oc/ref/ch05eliminationreacti
ons.html
EXPLAINING
THE
ELIMINATION
REACTIONS PRODUCING ALKENES
FROM SIMPLE HALOGENOALKANES.
ChemGuide. Retrieved on 10 April
2015,
from
http://www.chemguide.co.uk/mech
anisms/elim/elimtt.html
Introduction
Reactions.

to
Master

Elimination
Organic

Chemistry. Retrieved on 11 April

2015,
from
http://www.masterorganicchemistry
.com/2011/10/10/introduction-toelimination-reactions/